CN111875789A - Preparation method of polycarbonate dihydric alcohol with main chain containing benzene ring - Google Patents
Preparation method of polycarbonate dihydric alcohol with main chain containing benzene ring Download PDFInfo
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- CN111875789A CN111875789A CN202010818398.5A CN202010818398A CN111875789A CN 111875789 A CN111875789 A CN 111875789A CN 202010818398 A CN202010818398 A CN 202010818398A CN 111875789 A CN111875789 A CN 111875789A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/305—General preparatory processes using carbonates and alcohols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/40—Post-polymerisation treatment
- C08G64/406—Purifying; Drying
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Abstract
The invention provides a preparation method of polycarbonate diol with a main chain containing benzene rings, which comprises the steps of adding carbonate, dihydric phenol and a catalyst into a reaction bottle in a nitrogen atmosphere, heating for reaction, carrying out normal-pressure rectification operation, adding the dihydric alcohol, gradually removing low-boiling-point byproducts generated in the reaction process through a fractionating device, heating and carrying out reduced-pressure distillation after the distillate is removed, filtering and removing water to obtain a polycarbonate diol product containing the benzene rings.
Description
Technical Field
The invention belongs to the technical field of preparation of dihydric alcohol, and particularly relates to a preparation method of polycarbonate dihydric alcohol with a main chain containing a benzene ring.
Background
Polycarbonate diol is a special diol with excellent performance, a main chain is a repeated carbonate group and aliphatic methylene structure, two ends of the main chain are hydroxyl structures, and the polycarbonate diol is often used as a main raw material monomer for synthesizing polyurethane coatings, elastomers and finishing agents. Compared with the polyurethane product prepared from general synthetic raw materials of polyester and polyether diol, the polycarbonate polyurethane has the mechanical property of the polyester polyurethane and the flexibility of the polyether polyurethane, and provides wide application prospect for preparing the polyurethane product with high wear resistance, heat resistance and mechanical property.
At present, polycarbonate diol mainly takes one or two of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol and ethylene glycol as a synthetic raw material, is prepared by using one of diethyl carbonate, dimethyl carbonate and ethylene carbonate and micromolecule diol through ester exchange reaction, and the polycarbonate diol on the market mainly has two forms of viscous liquid and waxy solid at normal temperature. At present, polycarbonate diol is mainly imported by Japan Asahi chemical industry and Japan, and the price of the polycarbonate diol product is high, so that the further application of the polycarbonate diol product in polyurethane products is limited; in addition, the polyurethane material prepared by taking the existing common polycarbonate diol as an upstream raw material is generally low in temperature resistance and wear resistance, so that the use of downstream products is limited.
A benzene ring is introduced to the main chain of the polycarbonate diol, and a rigid group is introduced from the molecular structure, so that the performance of downstream products is improved. In the prior art, carbonate is generally reacted with dihydric phenol to directly introduce benzene rings on a main chain, but the preparation method directly introduces rigid benzene rings, and the following problems are generally existed:
(1) the reactivity is reduced due to steric hindrance effects;
(2) the use amount of the dihydric phenol is increased under the same proportion due to the large relative molecular mass of the dihydric phenol, so that the cost is greatly increased, and the dihydric phenol is not suitable for large-scale production;
(3) the brittleness of the polyurethane prepared by taking the polycarbonate dihydric alcohol as the raw material is also increased, and the mechanical property is correspondingly reduced after the benzene ring is excessively increased.
The invention provides a synthesis method for introducing a benzene ring structure into polycarbonate dihydric alcohol in a copolymerization mode, which has the advantages of simple synthesis process, good reproducibility, good controllability, reasonable cost and good performance of the prepared polyurethane, and belongs to the original invention.
Disclosure of Invention
In order to solve the problems in the prior art and further optimize the prior process, the invention provides a preparation method of polycarbonate diol with a benzene ring in a main chain, which aims to synthesize the polycarbonate diol with the benzene ring in the main chain by a copolymerization mode, introduce a benzene ring structure and improve the heat resistance and wear resistance of polyurethane prepared by taking the polycarbonate diol as a raw material in a molecular structure.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of polycarbonate diol with a main chain containing benzene rings is characterized by comprising the following steps:
(1) under the nitrogen atmosphere, firstly adding carbonic ester, dihydric phenol and a catalyst into a reaction bottle, heating for reaction, carrying out normal-pressure rectification operation, adding dihydric alcohol for continuous reaction, and gradually removing low-boiling-point byproducts generated in the reaction process through a fractionating device;
(2) and after the distillate is removed, continuously heating, carrying out reduced pressure distillation operation under the condition of extracting negative pressure, cooling the system to room temperature, and filtering and dewatering to obtain the polycarbonate diol product containing the benzene ring.
Wherein the molar ratio of the dihydric alcohol to the dihydric phenol is 5-9: 0.1-2;
the molar ratio of the total amount of the dihydric alcohol and the dihydric phenol to the carbonate is 1: 1.0-1.3;
the dosage of the catalyst is 0.1 to 0.6 percent of the total amount of the dihydric alcohol and the dihydric phenol;
preferably, the reaction temperature in the atmospheric distillation in the step (1) is 90-200 ℃, and the reaction time is 3-8 h;
preferably, in the normal-pressure rectification in the step (1), the adopted rectification column packing is a theta ring, the inner diameter of the rectification column is 4cm, and the height of the effective packing is 30 cm;
preferably, the reaction temperature during the reduced pressure distillation in the step (2) is 160-230 ℃, the reaction time is 1-5h, and the vacuum reaction pressure is lower than 4 KPa;
preferably, the carbonate is one of dimethyl carbonate, diethyl carbonate and ethylene carbonate;
preferably, the catalyst mainly comprises a titanium catalyst: one of n-butyl titanate, tetraisopropyl titanate, titanium dioxide, potassium titanium oxalate, titanium tetrabenzoate, titanium tartrate and titanium citrate; organic amine catalyst: one of triethylamine, tripropylamine, triethylenediamine, tetrabutylammonium bromide and 1, 2-di (trimethylammonium bromide) ethane; organic salt catalyst: one of triethoxy aluminum, triisopropoxy aluminum, sodium ethoxide and ethylene glycol antimony;
preferably, the diol may be one of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, and neopentyl glycol.
Preferably, the dihydric phenol is one of hydroquinone, 2, 6-dihydroxynaphthalene, 4-biphenol and 2, 2-bis (4-hydroxyphenyl) propane.
The main polycarbonate diol products and dihydric phenols thereof have the following structures:
on the basis of the ester exchange reaction of the polycarbonate dihydric alcohol, the polycarbonate dihydric alcohol containing the benzene ring is prepared by ternary polymerization of dialkyl carbonate, micromolecular dihydric alcohol and dihydric phenol, and the introduction of the dihydric phenol can reduce the production cost of the polycarbonate dihydric alcohol; on the other hand, the chemical resistance, the flexibility and the like of the polycarbonate diol are not influenced, and the mechanical property, the wear resistance and the heat resistance of the polycarbonate polyurethane product are further improved by introducing a benzene ring structure on the main chain.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the polycarbonate dihydric alcohol containing benzene rings prepared by the method has high product yield of 93-98 percent and the conversion rate of the glycol of 68-80 percent;
2. the polycarbonate dihydric alcohol containing benzene rings prepared by the method has high product purity, the product purity is 98.7-99.5%, and the acidity is 0.01-0.05 mgKOH/g;
3. the method for preparing the polycarbonate dihydric alcohol containing the benzene ring has the advantages of simple process, good reproducibility, good controllability and 7-12h of reaction time; the reaction temperature is within 90-190 ℃;
4. the dihydroxy dihydric phenol compound containing a benzene ring and a naphthalene structure is introduced to polycarbonate diol by an ester exchange method and is used as a basic upstream raw material to synthesize a polyurethane material, so that the polyurethane material has excellent heat resistance and mechanical properties;
the specific implementation mode is as follows:
the invention is further illustrated below with reference to specific examples.
Example 1
Under the protection of nitrogen, 124 g of diethyl carbonate and 11 g of hydroquinone are added into a 250mL four-neck flask, 0.372 g of catalyst of n-butyl titanate is added, the mixture is put into an oil bath kettle, a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) filled with a filler (theta ring) and a fractionating device are put on the bottle mouth, and normal-pressure rectification reaction is carried out at 130 ℃ for 2 hours until no distillate flows out; adding 82 g of 1, 4-butanediol, continuing to react for 3 hours until no fraction is distilled out, then heating to 180 ℃, continuously distilling out low-boiling-point intermediate byproducts, and finishing the distillation when no liquid is distilled out on a distillation head; and after the pressure reduction device is replaced, setting the vacuum degree to be 1 kPa, continuously vacuumizing and reacting for 2h at 180 ℃, and after the reaction is finished, filtering and removing water until the water content is within 1000ppm to obtain the polycarbonate diol.
The product mass of the prepared polycarbonate diol was 114g, the conversion and yield were 75% and 97%, respectively, and the final product purity was 99.2% and the acidity was 0.03 mgKOH/g.
Wherein, the conversion rate is calculated by calculating the conversion rate of hydroxyl to indirectly calculate the conversion rate of diol, and the calculation formula of the conversion rate is as follows: x is0Is the molar mass of the hydroxyl groups in the reaction monomers, X1Is the molar mass of hydroxyl groups reacted with the carbonate;
the yield is calculated by calculating the theoretical mass of the polycarbonate diol according to the reaction equation and then calculating according to the mass of the actually obtained target product, and the calculation formula is as follows: z is the quality of the product finally obtained by the reaction; z0Is the theoretical product quality.
Example 2
Under the protection of nitrogen, 100 g of dimethyl carbonate and 22 g of hydroquinone are added into a 250mL four-neck flask, 0.285 g of tetraisopropyl titanate serving as a catalyst is added into an oil bath kettle, a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) filled with a filler (theta ring) and a fractionating device are put on a bottle mouth, and normal-pressure rectification reaction is carried out at 90 ℃ for 3 hours until no fraction flows out; adding 73 g of 1, 4-butanediol, continuing to react for 3 hours until no fraction is distilled out, then heating to 160 ℃, continuously distilling out low-boiling point intermediate byproducts, and finishing the distillation when no liquid is distilled out on a distillation head; and after the pressure reduction device is replaced, setting the vacuum degree to be 2 kPa, continuously vacuumizing and reacting for 3h at 160 ℃, and after the reaction is finished, filtering and removing water until the water content is within 1000ppm to obtain the polycarbonate diol.
The product mass of the polycarbonate diol prepared was 115g, and the conversion and yield were 72% and 95%, respectively. The final product had a purity of 99.1% and an acidity of 0.01 mgKOH/g.
Example 3
Under the protection of nitrogen, adding 95 g of dimethyl carbonate and 18.6 g of 4, 4-biphenol into a 250mL four-neck flask, adding 0.248 triethylamine serving as a catalyst, putting the flask into an oil bath pot, putting a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) provided with a filler (theta ring) and a fractionating device on the mouth of the flask, carrying out normal-pressure rectification reaction at 90 ℃ for 3 hours until no distillate flows out; adding 106 g of 1, 6-hexanediol to continue reacting for 3 hours until no fraction is distilled out, heating to 160 ℃, continuously distilling out low-boiling-point intermediate byproducts, and finishing the distillation when no liquid is distilled out on a distillation head; and after the pressure reduction device is replaced, setting the vacuum degree to be 3 kPa, continuously vacuumizing and reacting for 5h at 160 ℃, and after the reaction is finished, filtering and removing water until the water content is within 1000ppm to obtain the polycarbonate diol.
The product mass of the polycarbonate diol prepared was 147g, and the conversion and yield were 80% and 98%, respectively. The purity of the final product was 98.7% and the acidity was 0.05 mgKOH/g.
Example 4
Under the protection of nitrogen, 100 g of dimethyl carbonate and 45.6 g of 2, 2-bis (4-hydroxyphenyl) propane are added into a 250mL four-neck flask, 0.288 g of catalyst sodium ethoxide is added, the mixture is put into an oil bath pot, a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) filled with a filler (theta ring) and a fractionating device are put on the bottle mouth, and the normal-pressure rectifying reaction is carried out at 90 ℃ for 3h until no distillate flows out; adding 72 g of 1, 4-butanediol, continuing to react for 3 hours until no fraction is distilled out, then heating to 170 ℃, continuously distilling out low-boiling intermediate byproducts, and finishing the distillation when no liquid is distilled out on a distillation head; after the pressure reduction device is replaced, the vacuum degree is set to be 1 kPa, the vacuum pumping reaction is continued for 2 hours at the temperature of 170 ℃, and after the reaction is finished, the mixture is filtered,Water removalUntil the water content is within 1000ppm, and then the polycarbonate dihydric alcohol is obtained.
The product mass of the polycarbonate diol prepared was 136g, and the conversion and yield were 68% and 95%, respectively. The final product had a purity of 99.0% and an acidity of 0.01 mgKOH/g.
Example 5
Under the protection of nitrogen, 106 g of diethyl carbonate and 18 g of 4, 4-biphenol are added into a 250mL four-neck flask, 0.452 g of tetraisopropyl titanate serving as a catalyst is added, the mixture is put into an oil bath kettle, a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) provided with a filler (theta ring) and a fractionating device are put on a bottle mouth, and normal-pressure rectification reaction is carried out at 130 ℃ for 4 hours until no distillate flows out; adding 95 g of 1, 6-hexanediol to continue reacting for 4 hours until no fraction flows out, heating to 190 ℃, continuously evaporating low-boiling-point intermediate byproducts, and ending the rectification when no liquid is evaporated on a fractionating head; and after the pressure reduction device is replaced, setting the vacuum degree to be 1 kPa, continuously vacuumizing and reacting for 3h at 190 ℃, and after the reaction is finished, filtering and removing water until the water content is within 1000ppm to obtain the polycarbonate diol.
The product mass of the polycarbonate diol prepared was 133g, and the conversion and yield were 74% and 98%, respectively. The final product had a purity of 99.5% and an acidity of 0.03 mgKOH/g.
Example 6
Under the protection of nitrogen, 103 g of diethyl carbonate and 6g of hydroquinone are added into a 250mL four-neck flask, 0.321 g of ethylene glycol antimony serving as a catalyst is added into the flask, the flask is put into an oil bath pot, a rectifying column (with the inner diameter of 4cm and the effective filler height of 30 cm) filled with a filler (theta ring) and a fractionating device are put on the mouth of the flask, and normal-pressure rectification reaction is carried out at 130 ℃ for 4 hours until no fraction flows out; then adding 101 g of 1, 4-cyclohexanedimethanol to continue reacting for 4 hours until no fraction is distilled out, then heating to 180 ℃, continuously distilling out low-boiling point intermediate byproducts, and finishing the distillation when no liquid is distilled out on a distillation head; and after the pressure reduction device is replaced, setting the vacuum degree to be 2 kPa, continuously vacuumizing and reacting for 4h at 180 ℃, and after the reaction is finished, filtering and dewatering until the water content is within 1000ppm to obtain the polycarbonate diol.
The product mass of the polycarbonate diol prepared was 114g, and the conversion and yield thereof were 71% and 93%, respectively. The purity of the final product was 99.2% and the acidity was 0.04 mgKOH/g.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art will understand that various changes, modifications and substitutions can be made without departing from the spirit and scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of polycarbonate diol with a main chain containing benzene rings is characterized by comprising the following steps:
(1) under the nitrogen atmosphere, firstly adding carbonic ester, dihydric phenol and a catalyst into a reaction bottle, heating for reaction, carrying out normal-pressure rectification operation, adding dihydric alcohol for continuous reaction, and gradually removing low-boiling-point byproducts generated in the reaction process through a fractionating device;
(2) and after the distillate is removed, continuously heating, carrying out reduced pressure distillation under the condition of extracting negative pressure, cooling the system to room temperature, and filtering and dewatering to obtain the polycarbonate diol product containing the benzene ring.
2. The method according to claim 1, wherein the molar ratio of the dihydric alcohol to the dihydric phenol is 5-9: 0.1-2.
3. The method according to claim 1, wherein the molar ratio of the total amount of the dihydric alcohol and the dihydric phenol to the carbonate is 1:1.0 to 1.3.
4. The method according to claim 1, wherein the catalyst is used in an amount of 0.1 to 0.6% based on the total amount of the dihydric alcohol and the dihydric phenol.
5. The preparation method according to claim 1, wherein the catalyst is mainly a titanium catalyst: one of n-butyl titanate, tetraisopropyl titanate, titanium dioxide, potassium titanium oxalate, titanium tetrabenzoate, titanium tartrate and titanium citrate; organic amine catalyst: one of triethylamine, tripropylamine, triethylenediamine, tetrabutylammonium bromide and 1, 2-di (trimethylammonium bromide) ethane; organic salt catalyst: aluminum triethoxide, aluminum triisopropoxide, sodium ethoxide and ethylene glycol antimony.
6. The method according to claim 1, wherein the carbonate is one of dimethyl carbonate, diethyl carbonate, and ethylene carbonate.
7. The method according to claim 1, wherein the diol is selected from the group consisting of 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 4-cyclohexanedimethanol, diethylene glycol, and neopentyl glycol.
8. The method according to claim 1, wherein the dihydric phenol is one of hydroquinone, 2, 6-dihydroxynaphthalene, 4-biphenyldiol, and 2, 2-bis (4-hydroxyphenyl) propane.
9. The preparation method according to claim 1, wherein the reaction temperature in the atmospheric distillation of the step (1) is 90-200 ℃, and the reaction time is 3-8 h;
10. the preparation method according to claim 1, characterized in that the atmospheric distillation in the step (1) adopts a theta ring as a rectifying column packing, the inner diameter of the rectifying column is 4cm, and the effective packing height is 30 cm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116120514A (en) * | 2022-12-29 | 2023-05-16 | 四川轻化工大学 | Bio-based transparent polyurethane and preparation method thereof |
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| CN101012307A (en) * | 2007-02-12 | 2007-08-08 | 江苏省化工研究所有限公司 | Method of preparing polycarbonate dihydric alcohol |
| KR20150125856A (en) * | 2014-04-30 | 2015-11-10 | 제일모직주식회사 | Polycarbonate resin, method for preparing the same, and article comprising the same |
| CN110615890A (en) * | 2018-06-19 | 2019-12-27 | 财团法人工业技术研究院 | Polycarbonate diols and polyurethanes formed therefrom |
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| US3030335A (en) * | 1959-01-02 | 1962-04-17 | Gen Electric | Aromatic polycarbonate reaction products |
| GB1026151A (en) * | 1962-11-26 | 1966-04-14 | Bayer Ag | Process for accelerating the transesterification process for the production of high molecular weight thermoplastic polycarbonates |
| CN101012307A (en) * | 2007-02-12 | 2007-08-08 | 江苏省化工研究所有限公司 | Method of preparing polycarbonate dihydric alcohol |
| KR20150125856A (en) * | 2014-04-30 | 2015-11-10 | 제일모직주식회사 | Polycarbonate resin, method for preparing the same, and article comprising the same |
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| CN116120514A (en) * | 2022-12-29 | 2023-05-16 | 四川轻化工大学 | Bio-based transparent polyurethane and preparation method thereof |
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